Inflammable composition containing red phosphorus



Patented July 14, 1953 UNITED s'm'ras INFLAIVHWABLE GOIWPOSITION CONTAININ G RED PHOSPHORUS 7 Martin S. Silver-stein, Camden, N. J. No Drawing. Original application January 2'1,

1944, Serial No. 519,949.

Divided and this application March 13, 1945, Serial No. 582,481

( Granted under Title 35, U. s. Code 1952), sec. 266) 2 Claims.

The invention described herein may be manufactured and used by or for the Government for governmental purposes, without the payment to me of any royalty thereon.

This invention relates to inflammable compositions of matter, such as ammunition primer compositions, including red phosphorus and a solid oxidizing agent for red phosphorus.

It has been proposed to use red phosphorus in small arms primer compositions mixed with such substances as barium nitrate, antimony sulphide and lead peroxide. Such primer compositions have been found to offer the advantages of giving uniform ballistic results as well as being noncorrosive. Red phosphorus is also extensively used for match heads as well as in striking surfaces for matches.

However, when compounded with oxidizing agents, the phosphorus is exposed to increased oxidation effects. is produced a liquid which is probably an aqueous solution of phosphorus acids and probably, ultimately, phosphoric acid. It is the presence of this liquid which is disadvantageous to the aforementioned uses of red phosphorus in that it renders the phosphorus more difficult to ignite.

The present invention makes use of red phosphorus which has been prepared or treated in accordance with the process claimed in my copending application Ser. No. 519,949, filed January 27, 1944. The present application is a division of said application and a continuation-m part of my co-pending application Ser. No. 410,054 filed SeptemberS, 1941, now abandoned.

The process or method comprises a preliminary period of deliberate oxidation and the removal of the products of this reaction before using the phosphorus.

Analyses of many samples of red phosphorus of commerce from various sources of supply have revealed that all of them contained compounds of iron and compounds of other metals, such as copper. These compounds are present in comparatively small amounts, and their amounts vary. Iron compounds, for example, in red phosphorus sold on the .market are present in amounts which roughly vary from 200 to 700 parts of iron (as Fe) per million parts of substantially dry pulverulent red phosphorus. As is well known, red phosphorus appears in commerce as a pulverulent material which, when first prepared or fresh, is a substantially dry powder, but it slowly becomes moist if freely exposed to the atmosphere or if it is kept in a container which is not tightly closed to prevent access of the atmosphere,

During such oxidation there When the pulverulent red phosphorus of commerce is treated according to the process of my above mentioned co-pending applications, the resulting substantially dry pulverulent red phosphorus contains very much less of iron than the red phosphorus used as starting materials. The iron compound content (calculated as Fe) of the red phosphorus after treatment according to the process of said applications is reduced to from 5 to 30 parts of iron per million parts of substantially dry pulverulent red phosphorus.

It is due principally to the removal of iron that red phosphorus prepared according to the process of said applications is more resistant to oxidation than red phosphorus sold on the market. The iron compounds, which are removed from the red phosphorus by treatment according to the process of said applications, act to catalyze the oxidation of the red phosphorus if permitted to remain therein, particularly if the red phosphorus is closely associated with a solid oxidizing agent, as is the case of the inflammable primer compositions described herein. The above-mentioned small quantities of metal compounds associated with red phosphorus probably originate from the metallic equipment used in its preparation.

The following examples of the practice of the method or process of said applications, and the preparation of compositions according to the present invention are given below:

Example I Commercial red phosphorus is placed in porcelam dishes and exposed in a chamber which is maintained at relative humidity and 40 C. ior a period of live days after which the material is dispersed in ten times its weight of water for one hour and the red phosphorus is filtered ofi and washed with water until the washings are no longer acid to litmus paper. The material is then dried in a vacuum oven and is ready for use. The oxidation of the red phosphorus was reduced to 10% of its original value by this preliminary period of oxidation. The iron content of the treated phosphorus was reduced to 17 parts of non (calculated as Fe) per million parts of dry product.

Example II The process according to this example is the same as in Example I with the exception that the preliminary oxidation is continued for a period of 19 days instead of for 5 days. In this instance the oxidation of the red phosphorus was reduced to 8% of its original value. The iron content was reduced to 10 parts of iron per million parts of dry product,

Example III The process according to this example is the same as in Examples I and II except that after the preliminary oxidation, either before or after the washing with water to remove acid, the mass of red phosphorus is subjected to any suitable :phorus process to remove particles of red phosphorus less than 10 microns in diameter. Any suitablesedimentation or floating process may be used to accomplish this separation. The product from which the particles of less than 10 microns in diameter have been removed is subjected to filtration, if necessary, and is washed? with water to remove acid, if any acid is still present'after'the' The said acid freel.

said separation of particles.

at 55-60 C. at a pressure of approximately 29 inches of mercury below atmospheric pressure.

The iron content of the final dry product of red phosphorus was lowered 'by"treatment according to this example to 5 parts of iron (calculated as Fe) per million parts of red phos- Example V I The process according to this example is the same, as in Example IV with the exception that the preliminary oxidation is to continue for a period of only 2 days instead of 15 days and particles less than microns in diameter are not product is then dried in a vacuum ovenias in Example I, and is then ready for use. The iron content of the final dry. products obtained ac'- Example IV The preoxidation or partial oxidation of the red phosphorus of commerce is carried out by subjecting it, in pulverulent or finely divided form, to the oxidizing influence of hot watermoist atmospheric air or gaseous oxygen or oxygen enriched air. Air ranging in temperature from about 40 C. to'about 90 C. and in relative humidity from about 50 to about 100 per cent may be used. The following procedure has given a final product of very good stability or resistance to oxidation.

Red phosphorus of commerce, in pulverulent form, and of about 200 to 250 parts of iron per million parts of red phosphorus was used as the starting material. This was spread out in layers of about 1% inch thickness in glass or enamel trays and exposed to an atmosphere of atmospheric air, or a current of atmospheric air, at atmospheric pressure, at 40 C. with a relative humidity of 90 per cent for a period of 15 days; At the end of this oxidation period of 15 days the material was washed free of acids by dispersing it in water, filtering with suction on a Buchner funnel and washing the material in the funnel until the filtrate was no longer acid to litmus paper.

The acid free material was then subjected to a separation procedure to remove substantially all particles of red phosphorus less than 10 microns in diameter. This separation may be accomplished by means of any suitable elutriation, sedimention or flotation procedure. Such procedures are well known in the art of separating or classifying pulverulent solid material and do not require specific description here. The separation may be conducted so as to effect the separation of substantially all of the particles less than 10 microns in diameter or these may be separated for the most part.

After this removal of particles of less than 10 microns in diameter, the material is again suction filtered if it still contains water that can be removed by filtering with suction. The finely divided material consisting of particles of 10 microns and above is then dried in a vacuum oven removed. In'this instance, the oxidation of the redphosphorus was reduced to approximately 30% of its original value. The iron content was reduced to 30 parts of iron per million parts of dry products.

The steps of treating the red phosphorus according to this example, are the same as Example IV except that the period of preoxidation or partial oxidation is 20 days instead of 15 days. The stability and iron content of the final product are about the same as the final product obtained according to Example IV.

Example VII The pulverulent red phosphorus prepared according to any of the preceding examples may be formed into inflammable compositions by mixing it with a solid oxidizing agent in finely divided condition. The following oxidizing agents may be used according to the intended use: potassium nitrate, barium nitrate, stron- 1: Stevenson, and to prepare propellant charges according to U. S. Patent No. 2,206,0 i8 granted July 2, 1940, to Ernest R. Rechel and Thomas Stevenson.

Primers prepared according to the above-mentioned patent of Pritham, Rechel, and Stevenson, utilizing red phosphorus prepared according to the preceding examples, are much more stable and resistant to oxidation influences than when red phosphorus found on the market is used. (End of Example VII.)

It is to be noted that the present invention increases the resistance of red phosphorus to oxidation by lowering the iron content thereof to values below the already low values of the iron content of red phosphorus found on the market or in commerce. As pointed out above, this iron content acts as a catalyst to increase or accelerate the oxidation rate. By reducing the iron content to low values, the oxidation rate is depressed or lowered. Utilizing the procedure of 5 invention is not intended to be limited thereby, but only within the scope of the appended claims, since other uses and specific methods will be readily apparent to those skilled in the art.

It has also been found that red phosphorus found on the market oxidizes to an undesirable degree even in the absence of added oxidizing agents. The process of the above-mentioned applications is therefore useful regardless of whether the red phosphorus is to be compounded with other agents or used per so.

I claim:

1. An inflammable composition comprising a solid oxidizing agent for red phosphorus and red phosphorus containing not more than thirty parts of iron per million parts of red phosphorus. 1

' 2. A primer 'for ammunition comprising a flame-producing composition including a solid oxidizing agent for red phosphorus, and red phosphorus containing not more than thirty parts of iron per million parts of red phosphorus.

MARTIN S. SILVERSTEIN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,050,796 Kershbaum et a1. Aug. 11, 1936 2,194,480 Pritham 1.. Mar. 26, 1940 2,359,243 Pernert Sept. 26, 1944 FOREIGN PATENTS Number Country Date 13,695 Great Britain of 1851 356,809 Germany July 31, 1922 370,379 Germany Mar. 3, 1923 OTHER REFERENCES Shalabanov C. A., vol. 26, 1932, page 1729. Mellor, Inorg. and Theoret. Chem, vol. 8, page 743. (Copy in Div. 59.) 

1. AN INFLAMMABLE COMPOSITION COMPRRISING A SOLID OXIDIZING AGENT FOR RED PHOSPHORUS AND RED PHOSPHORUS CONTAINING NOT MORE THAN THIRTY PARTS OF IRON PER MILLION PARTS OF RED PHOSPHORUS. 